Gasoline containing anti-icing additive



United States Patent Ofiice 3,440,029

Patented Apr. 22, 1969 contact with water and they do not readily form gasoline- 3 440,029 GASOLINE ONT N NG ANTI ICING ADDITIVE water emulsions. The latter properties are partlcularly luable because asoline ordinaril em in ont ct John C. Little and James P. West Midland Mich. asy es a signors to The Dow Chemical Company, Midfand, with water dimng Its haniihng i i h Mich.,acorporation of D l The practice of the lnvention is illustrated by the No Drawing. Filed May 20, 1964, Ser. No. 369,018 followmg examples- US. CL 44-31517. Cl- C101 1/22, C076 91/16 2 Claims PREPARATION OF ADDITIVES I The hydroxy compound, ROH, was condensed with al- This invention relates to gasolines containing an antikylene oxide in the desired proportion bythe use of NaOH icing additive to inhibit engine stalling. as a catalyst, this being a well known procedure. The Oxy- The stalling of gasolines due to carburetor icing in alkylated material was then cyanoethylated by reaction cool, humid weather is a well known phenomenon and with acrylonitrile in a well known reaction as described,

various fuel additives have been proposed to inhibit such for instance, by Bruson in US. Patent 2,280,792. The stalling (see, for instance, US. Patents 3,115,397, 3,115,- cyanoethyl ether was then hydrogenated with Ru on C 399 and 3,115,400). a or with Raney nickel at about 100-125 C. and a hydro- The present invention provides a new and highly efiecgen pressure of 700-1400 p.s.i. Solvents used were methative class of anti-icing additives for use in gasoline which 1101 or aqueous ammonia (28% otherwise might promote carburetor icing and resultant Several gasoline additives were evaluated in a 6-cylinengine stalling. These additives are gasoline-soluble comder automobile engine to which the fuel and saturated pounds having the formula air (100% humidity) were fed at 40 F. The carburetor was insulated to prevent its being warmed -b engine heat. (CmH2mO)x (CH2o)y CpH2P NH2 The fuel was a commercial straight-run .gas line to which wherein R is a hydrocarbon radical of 824 carbon atoms, was added 15% of isopentane and 5% of butane. It had an m, n and p are integers 2-4, and x and y are integers 0-40, ASTM boiling range of 10% at 110 F., 50% at 167 F. their sum being 050. and 90% at 260 F.

The preferred additives are these having the above The IPA Rating is an arbitrary scale based on the formula wherein R contains 12-18 carbon atoms, In and p effectiveness of isopropyl alcohol as a de-icer. The conare 2-3, x is 0-20 and y is zero. centration of isopropyl alcohol which gave the maximum y of the Compounds having the above formula protection was 1.5% by volume, and this was set at 100. are known and the others can be made by substitutlon Thu a rating of 50 means that the compound at the of the pp p reactants in known processes Thus, concentration shown was half as effective as 1.5% of In g l, the compounds can be convenrently m y isopropyl alcohol, a rating of 200 means twice the effeccondensing a hydroxy compound, ROH, with an alkylene ti g, t

oxide, C H O, or a mixture of such oxides, then, option- In the test itself, after the engine was started cold, it ally, with a second alkylene oxide, c n o, or mixture, was operated for 30 seconds at 2000 r.p.m. and then 30 and finally attaching the terminal amino group by either seconds at idle to constitute one cycle. Without stopping reductive amination (U.S. Patents 2,754,330 and 2,928,- the engine these high speed-low speed cycles of one 877) or by cyanoethylation followed by hydrogenation mintute each were repeated until stalling occurred. The

(U.S. Patent 2,280,792; Nystrom and Brone, J. larger the number of cycles that could be repeated without Chem. Soc., 70, 3738 (1948)). According to another synstalling, the higher the IPA rating. Thus, with no additive, thesis, ROH or an oxyalkylated derivative thereof is rethe engine stalled after the first cycle, 1% isopropyl alacted with bis(2-chloroethyl)ether and alkali to make a cohol gave 3 cycles before stalling and 1.5% isopropyl chlorine-terminated compound. The latter is then reacted alcohol gave 5 cycles before stalling. A maximum of with ammonia to produce the amine-terminated final prod- 14 cycles were .run. At a concentration of 200 p.p.m., uct. Other syntheses will be obvious to those skilled in the the compound C H C H O(C H O) (CH NH preart. vented stalling through all 14 cycles and it was thus In choosing the particular compound to be used it is given a rating of 230+, indicating that it was greater than preferable to maintain a balance between the hydrophobic 2.3 times as effective as 1.5 isopropyl alcohol.

and the hydrophylic moieties therein. Thus, when R is Results of these tests are shown in Table I.

TABLE I.EFFEOTIVENESS 0F ADDITIVES R0(Gammon- 0.112.,0), o,,H2,,NH2

Additive IPA rating at concentration shown Example R m x n y p 2% 1.5% 1.0% 0.5% 200 100 50 25 12.5

p.p.m. p.p.m. p.p.m. p.p.m. p.p.m.

1 Nonylphenyl 2 4 0 3 230+ 170 110 93 67 2 n-O ctadecyl 0 0 3 140 87 80 47 3 Isopropyl alcohol. 80 100 67 33 highly hydrophobic, m and n should be mostly or exclu- Several typical amine additives of the invention were sively 2; i.e., oxyethylene radicals should predominate. evaluated as carburetor-icing inhibitors by adding them Also, the number of such groups is preferably at least to a gasoline fuel having pronounced tendency to cause 4. On the other hand, when R is less hydrophobic, the carburetor-icing and then feeding the fuel composition to oxyalkylene radicals are preferably less hydrophylic in a bench-mounted carburetor operated by suction from an nature; i.e., they are predominantly oxypropylene and/or air aspirator. This apparatus permitted close control of oxybutylene, with at most a small proportion of oxyethylflow r t mper ures, humldlty, etc. and lncluded a cue radicals, wire screen upon which the ice collected. The pressure In addition to being effective carburetor de-icers, the drop across this screen was continuously indicated by a additives of the invention have the further advantages manometer and was a convenient indicator of the degree that they are compatible with other gasoline additives, of icing produced with each fuel. By holding all other such as anti-knock additives, antioxidants, corrosion invariables constant and feeding successive portions of the hibitors and the like, they are not readily extracted by same gasoline containing a different additive in each portion, a direct cornparison of the effectiveness of the various additives was made. The results of such tests, in which air at 37 F. and 90% relative humidity was used, are shown in Table II. The numerical ratings are based on an arbitrary numerical scale 1-10 wherein the fuel with no additive rated 2 and that containing 1.5% of isopropyl alcohol rated 5.

TABLE II.EFFECTIVENESS OF ADDITIVES R(cmHzmo)x(CnH2n )yp 2n 2 Additive Rating 1 at concentration shown,

Example p.p.m.

R m x n y p 200 100 50 25 4 Octylphenyl 2 1 O 3 10 7 Nonylphenyl 2 2 0 3 1O 5 G d0 2 4 0 3 10 7 5 2 9 0 3 10 10 7 5 2 0 3 8 2 3 0 2 6 2 5 0 2 7 0 0 3 8 3 0 O 3 10 6 0 0 3 8 6 14 n-OctadecyL. 0 0 3 8 7 3 16 n-D0decyl. 2 4.5 0 3 9 8 2 l6 do 2 9. 5 0 3 10 7 l The dashes indicate that no test was run.

In additives of the above formula wherein y is greater than zero, it is generally preferred that m be 3 or 4, that n be 2 and that y exceed x. While it is preferred that R be alkylphenyl or alkyl, it may also be phenylalkyl or other hydrocarbon. Table III shows some typical compounds having the above formula that are effective as gasoline anti-icing additives.

TABLE III R m x n y p Octylpheuyl 3 3 2 5 3 DodecylpheuyL 4 2 2 6 2 Pentadecylphenyl 2 0 4 Octadecylphenyl 2 40 0 3 Nonyl 1 4 5 2 15 2 Nonyl 3 15 2 3 Pentadecyl. 3 8 2 20 4 Phenyl 4 0 2 10 3 Benzyl. 3 3 2 12 2 Phenethyl. 2 l0 3 1 3 4-octylbenzyl 2 16 0 3 In the additives of the invention the configuration of the alkyl and alkylene radicals is of little significance. Thus, they may be primary, secondary or tertiary, straight- RO(C H O) C H NH wherein R is an alkylphenyl radical containing 14-18 carbon atoms and x is 1-20.

2. The composition of claim 1 wherein the alkylphenyl radical is nonylphenyl and x is 4.

References Cited UNITED STATES PATENTS 3,063,819 11/1962 Watt et al. 44-72 3,115,400 12/1963 Marsh et a1 44-72 3,238,277 3/1966 Sigan et a1. 4456 DANIEL E. WYMAN, Primary Examiner.

W. H. CANNON, Assistant Examiner.

US. Cl. X.R. 

1. AN IMPROVED GASOLINE MOTOR FUEL COMPOSITION COMPRISING: (1) A MAJOR PROPORTION OF A GASOLINE THAT NORMALLY TENDS TO PROMOTE STALLING OF INTERNAL COMBUSTION ENGINES BY CARBURETOR ICING, AND (2) A SMALL BUT EFFECTIVE PROPORTION OF A GASOLINE-SOLUBLE ANTI-ICING ADDITIVE HAVING THE FORMULA 